Aryloxydihydronorpolycyclopentadienes



' diene the simplest; compounds of Patented Oct. 2, 1945 p g 7 2,385,7877 Ammo:nmmrnnoNoRroLm'roam a E I NE g a Herman A. Bruson,Phlladelphlafla assignor to The Resinous Products Chc'mi Philadelphia,la.,

cal Company,

a corporationoi. Delaware No Drawing. Application February 20, 1943, 1

Serial No.476,642

Foam... (01. zoo-i612? I This invention'relates to aryloxydihydronorpolycyclopentadienes and to a process for their.

preparation from monohydric phenols and poly-.

cyclopentadienes having two double bonds per molecule. 1

It has been shown-that 'phendls' condense with indene, coumarone, orcoal tar fractions which are rich'in lndene and coumarone and which mayalso contain varying amounts oi dicyclopentadiene (Rivkin and Sheehan,J. Ind. Eng. Chem 30, 1228 (1939)). As the result tion, there are formedresins.

It has been found however, that instead of resins there'may be obtainedwell defined chem ical compounds by reacting a polycyclopentahaving twodouble bonds per molecule with a monohydrlc phenol inthe condensingagent. The addition of one reactant rangement of the terminalendomethylene cycle of the polycyclopentadiene, are formed aryl ethersof a nucleus belonging .to a new ring system, "norpolycyclopentadieneand which will be more fully characterized hereinafter.

reaction involves both veniently illustrated with the reaction involvingactants. Thus, phenol reacts with dicyclopentadiene in the presence ofboron. trifluoride,

other acidic condensing agent,

sulfuric acid, or according to the following equation:

probable. ,7

Similarly, tricyclopentadiene, tetracyclopentadlene,pentacyclopentadiene, and "homologues and isomersthereof, individuallyor in mixtures, may be reacted with a monohydric phenol to give arylothers. The polycyclopentadienes having two double bonds per moleculeare obtained as presence of an acidic,

to another and rear-' which 'is here designated both classes of, re-

the product is the more 10 of the condense-i crystalline solids heatingcyclopentadiene, at

150 2010", 0. in a closedvessel.

' They have the followinggeneral structure: 5 'yj where nis a numberfrom zero a smallwhole number, such asl, 2 or 3.-v

The products of this inventioa'are acid catalyzed',addition-rearrangement products from a, phenol and a polycyclopentadienehaving two double bonds and one; to fourv I cycles per molecule. Theyare aryldihydronor- Ass. result, there The addition-rearrangementreaction is con- ;a cyclopenteno grou and Ar is an aryl nucleus...

In place of phenol itselt used in the above illusaralkyl, aryl,

polycyclopentadienyl ethers having thegeneral formula; k

wherein CaHl is a propylene group which'in con-1 Junctionwith theadjoining, carbon atoms forms such as a phenol having one or more alkyl,

cycloalkyl, srv o y. 1 ai0-.,acy v I Suitable phenols include theortho-, meta-, and

tration, there may be used fasubstituted phenol,

para-cresols, the 'ch lorophenols, including 1 both. monoandpoly-chloro-substituted phenols, the 'bromophenols, chlorocresols,bromocresols, tert.-';

phenol," diisobutyl phenol,

ethoxyethyl phenol, p-naphthol, p-phenyl phenol, cyclohexyl phenol,benzyl phenol, acetyl phenol or other butyl phenol, octyl dodecylphenol,.-,methoxyph enol,-

monohydric phenol.

To promotev the reaction betweemphenol and polycyclopentadiene, there isused an acidic condensing agent, typical or which are sulturlc'acid,sulfuric acid esters, v suli'onic'acids, such as toluene sulfonic acidor butyl sultonic acid, hydrogen fluoride, boron trifluoride andoxygenated compounds, such as borontrifluoride complexes of alcohols,ethers,

fluoride, coordination complexes of boron triesters, ketones,'aldehydes,wa'ter,-etc-., Friedelg Crafts antimony, or titanium chlorides,tetraphosphoric v catalysts such as aluminum, v,iron,

acid and the like.

endomethylene 7 alkoxy, alkoxyalkyl, or similar substltuents.-,

such as ethyllacid sulfate,

:Amongthe most useful of all the catalysts or;

acidic condensing agents are boron trifluoride and its. coordinationcomplexes of oxygenated compounds. Typicalcomplexes from ethers are.BF3.C2H5OC2H5 and BF3.C4H9O-C4H9.

} These are colorless, fuming liquids which are readily assays with hotwater and with soda solution. The oil was separated and dried and thenmixed with 1 per cent. 'ofits weight of dry sodium carbonate anddistilled in vacuo. The fraction boiling at 140-l50' C./l mm. was a paleyellow oil.

,- tained in an amount of 98 parts, which gradsoluble in the reactionmixture, do not form', undesirable by-products, are readily removed uponI completion of the reaction by a simple operation such as washing withwater or washing with a solution of an alkaline agent, such as sodaash..

Other typicalcomplexes include such products as where a: is one or two,BFaChHsOH, etc.

.The quantity of quired is generally small. Amounts varying from 1 jtoper cent. of the weights of thereactants are usually entirelysatisfactory, although decreased or increased amounts may be used,commonly without marked advantage. The acidic condensing agent maydesirably be removed folacidic" condensing agent reually solidified toacrystalline mass. After recrystallization from methanol and bleachingwith charcoal, the product, identified as thephenoxydihydronordicyclopentadiene, formed colorless 1 crystals,melting, when pure, at 70-71 C., and

lowing the reaction by extraction or neutraliza I tion.

mixed in any desired order. Since the reactions are exothermic, it isoften advisableto cool the The reactants and condensing agent maybereaction mixture, particularly at the start,

and/or to combine reactants or catalyst slowly, and/or to employasuitable solvent or diluent,

' such as petroleum naphtha,-or a chlorinated solvent, such as ethylenedichloride, chloroform,

carbon tetrachloride, or the like.

are not themselves soluble in the polycyclopentadienes. V v

The reaction is performed at temperatures be tween about 0 and 100C.,ithe range of 40 Solvents are I ofparticular value in the .case ofphenols which C. being preferred. In general, it is best to keep thereaction mixture below 85 Cfiat the start and'use higher temperaturesonly to complete the reaction.

Under the conditions discussed, only one double bond of the twooriginally present in the polycyclopentadienes here described reactswith'the hydroxyl group of the. phenol. The reaction takes "place onlyat parent equivalency of the 45. V the double bond of the terminalendometh'ylene cycle in spite of the apdouble bonds in the parentpolycyclopentadiene. At the same time, I

under the influence or the acidic condensing agent, the aforementionedrearrangementtakes place, forming new cycles, the structure of which 204 parts under reduced pressure.

jnordicyclopentadienecame over as a colorless oiL- at l40-'-'153C./l-'-2 mm. in a yield of 95 parts.

on'standhaving the probable formula:

. CH\ chi J pholeum") of dicyclopentadiene was fifteen'minuteswhile, thereaction temperature;

was maintained at 35-40 C. by cooling.

The mixture was then stirred for aboutone and one-half hours until theexothermal reac tion ceased. I Finally, the mixture was-heated for twohours'iat 40-50 C. to complete the reaction. The thick, darkliquid waswashed with hot water and with soda solution and wasdistilled Thephenoxydihydro- 1 It solidified to a white crystalline mass ing and,after recrystallization, from methanol, formed colorless needles meltingat 702 11 0. (c) To a solution of lpart of BF: in 98 parts of phenol,132 parts of dicyclopentadlene was added dropwise while the mixture wasstirred and cooled so'that' the temperature did not ex-, ceed 75 C. Theproduct'was stirred for eight hours longer, then washed with hot water,neutralized with soda, dried, and distilled as above.

The yield of phenoxydihydronordicyclopentadienewas parts, v

- Example 2,

A'mixture consisting of .108 parts of orthovcresol and 132 parts ofdicyclopentadiene was stirred while 18 parts of 98% sulfuric acid washas been established to be that shownin the above illustrative example.The resulting 'aryloxydihydron'orpolycyclopentadienes are useful asinsecticides, aszsolvents, as"

plasticizers, and as intermediates; for preparing drugs, resins,sulionated' wetting agents, etc. 7 The residual double bond of theterminal five-mem bered cycle lsstili capableof reactingwith hydrogen,chlorine, bromine, iodine chloride, iodine bromide, thiocyanogen, etc.Iv

The invention is further illustrated by the following examples, glvingdetails of the prepara-' tion of the new ethers. Parts are by weight. I

- Ercample 1 Y (a) To a stirred mixture of 132 parts ofdic'yclopentadiene and 94 parts of phenol, there was added 'dropwlseduring thirty minutes 18 parts of 98% sulfuric acid while the reactionmixture iwas maintained at 28-32 C. by watercooling. The 'mixture'wasstirred thereafter for two hours,

then poured into hot water. The oil layer which formed was separated andwashed thoroughly 1 added drop'wise thereto during thirty minutes at30-31 C. The mixture was stirred for two hours longer, then washed anddistilled as described in Example 1. Theo-methyl-phenoxydihydronordicyclopentadiene distilled over at C./2 mm.as a yellow oil which crystallized on standing. After recrystallizationfromimethanol and bleaching with charcoal, it formed colorless crystals.melting at 4'1-48 C. and having the probable formula:

' on on: on, l n

In a similar manner, meta cresol gave the correspondingm-methylphenoxydihydronordicyclopentadiene, which boiled at l65-l67(7.13.5 mm.

" and which crystallized from ethanol in colorless needles having amelting point of 69' C.

, Example 3 A mixture of 132 parts of dicyclopentadiene iK ji Example 4To a solution of 132 parts of dicyclopentadiene, 260 parts of ethylenedichloride,and 150 parts of para-tertiary butyl phenol, there was addeddropwise 18 parts of 98% sulfuricacid during the course or flity minuteswhile the, reactionjtemperature was held at 28-32 C. The mixture wasthen stirred for eight hours at 3045 C..and poured into hot water. Theoil-layer was washed several times with hot water, oncewith hot di lutesoda solution, and finally with water. 'The ethylene dichloride wasevaporated ofhandthe residual oil in an amount'ot 2l8 -parts distilledat 3 mm. The p-tert.-butylphenoxydihydronordicyclopentadiene distilledover at 195-205 C./3 mm. as a pale yellow viscous oil. .Uponredistillation at 1 mm., it came over at 180 (Land formed a very paleyellow thick oil.

Example 5 To a stirred solution of 124 parts of guaicol and 10 parts ofboron trifluoride-diethyl ether complex (BFs-CzHr-O-CzHs), there wasadded dropwise 132 parts of dicyclopentadienev during the course ofwonehour while the reaction mixture was held at 29-32 C. by cooling. Themixture was then stirred for five hours at room temperature, washedwith'hot water, and with soda solution, and distilled in vacuo. Theguai'coxydihydronordicyclopentadiene, having the probable formula:

on on, c L .06 on distilled at ma iac c./2 mm. as a colorless viscouscoil. The yield was 121 parts. lllponredistillation, it boiled atTIT-176 C./2:mm.

Example 6 To a stirred solution of 122 parts of p-ethyl phenol and 132parts of dicyclopentadiene at 83' (1., therewas gradually added 20 partsof boron trifluoride-diethyl ether complex during the course oftwenty-minutes. After about ten parts had been added, a vigorousexothermic reaction 4 set inwhich raised the temperature to about C. andnecessitated cooling with ice to moderate the reaction. The mixture wasstirred for ilve hours longer, then washed with hot water and,

with soda, and distilled in vacuo. The product, p e t h ylphenoxydihydronordicyclopentadiene,

distilled at 175 C./ 2 mm. as a colorless viscous oil ina yield 0! 70parts.

Example 7 To a stirred solution of 128 parts of p-chlorophenol and 10'parts of boron trifluoride diethyl ether complex, there was graduallyadded 132 parts 01 dicyclopentadiene while the mixture was cooled andthe reaction temperature maintained at 30-40 C. The mixture was stirredthereafter for three hours and then washed with hot. water and with sodasolution. An oil layer was separated, dried, and distilled in vacuo. The

product, p-chlorophenoxydihydronordioyclopentadiene,distilled at'165-175'C./2 mm. as a. viscous,-paleyellow oil in a yield 01 10'!parts. Upon redistillation, it boiled at 169-174C./ 2 mm. and solidifiedto a crystalline mass which, after recrystallization from methanol,formed colorless crystals melting at 55 C.

Example 8 To'a stirred solution of 122 parts of 1,3 ,5 -xylenol and 132parts of dicyclopentadiene at 40 0., there was gradually added 10 partsof boron tri-.

'fluoride-diethyl ether complex. during which time the temperature roseto C. The mixture was stirred ,ior three and one-quarter hours at roomtemperature, washed with hot water and with soda. solution, anddistilledin vacuo. The product, 3,5-dimethylphenoxydihydronordicyclopentadiene,distilled at 1'75-180 C./3 mm. as a r v colorless oil in a yield of 136parts.

, cyclopentadiene, distilled at 190-195 C./3 mm.

"distlllediat 230-235 C./2

Example 9 To a stirred solution of 49 parts of p-bromophenol and 3'7parts 01 dicyclopentadiene at 35 0., there was added 1 ,part of borontrifluoridediethyl ether complex. The exothermic reaction raisedthereaction mixture to '75 C. The viscousflmass obtained was washed withhot water and with soda solution,- separated therefrom, taken up intoluene, and distilled in vacuo. The reaction product,p-bromophenoxydihydronordi as a viscous oil which crystallized, onstanding, in a yield of 46 parts. After recrystallization 'irommethanol, it formed colorless crystals melt ing at 72 C.

Example 10 To a stirred solution 01! 55 parts 01 p-benzylphenol, 39.8parts of dicyclopentadiene and parts of ethylenedichloride, 2 parts ofboron tri fluoride-diethyl ethe complex was added.. An

exothermic reaction set in which was controlled at 30-35 C. by cooling.The mixture was then stirred 'ior five hours -at room temperature,

washed with water, then with soda solution,

dried, and distilled in vacuo. The resulting p --..;b 'e'nzzylphenoxydihydronordicyclopentadiene ina yield of parts.

Example 11' A mixture 0149.2 parts of p-tertiary-amylpenol. 39.8 partsof dicyclopentadiene, and .2 parts of BFa-diethyl ether complex wasprocessed mm. as a viscous oil i r described in Example. 10. Theresulting ptilled as a viscous oil at 210-22'0 C./ 2 mm.

After this product had been 7 .190--200 C./3 mm. as'a'colo'rless -86parts.

tert. amylphenoxydihydronordicyclopentadiene boiled at 192-194 c./a mm.

Example 12 p I mixture 01 52.8 parts'of p-cyclohexylphenol,

39.6 parts of dicyclopentadiene, and 2 parts of BFa-diethyl ethercomplex was processed as de-- scribed in Example 10. The resultingp-cyclohe x yl ph e no x -ydihydronordicyclopentadiene= boiled at 2122-161C./2"mm."as'a viscous "color-'- less oil. Upon standing zlnlceecold ethanol, it gradually crystallizedand formed colorless crys- Toa stirred solution '01-'72 part sof -naphthol,

traces of insolublep-phenylphenol. The filtrate waswashed, dried, anddistilled as in Example.

- dicyclopentadiene distilled at.22 5230 C./2

100 parts of ethylene dichlorlde, and 66 parts of dicyclopentadiene,cooledto' C.,' 3 parts of I Ettample 14 To'a stirred solution of 114parts of 2,4- dichlorophenol, 130 parts of ethylene dichloride, V and 2parts of BFa-diethyl ether complex, there wasi added dropwise 92.4 partsof dicyclopentadiene at -35'C. The mixture was then stirred for threehours at C. It was washed with water and'with; soda solution, dried;and'distilled in vacuo. The qresulti'ng"2,4-dichlorophenoxy -jdihydronordicyclopentadiene distilled over at Upon" redistillation, itboiled at 1'75"- l C./2 mm. 1V g H Ezramplef15 f To aistlrredsolution-of 59.3 parts of chlorophenol,"130 parts of ethylenedichloride,

7 and 2 parts of BFe-diethyl ether'complex, there 'wasadded' dropwise39.6 parts of dicyclopentadiene at 25 C. The mixture was stirred 'at'25C. for three hours, then washed with water and with soda solution. Theoil was separated, dried,

and'dlstilled' in vacuo. The resulting 2,4,5-tri- 2,4,5-tri- Example 17.To a stirred suspension of parts of p-phenylphenol, 500 parts ofethylene dichloride, and 3 parts of 'BFs-diethyl ether complex, 66parts'of dicyclopentadiene was added. The temperature rose to 38 C. Themixture was stirred for five hours without cooling and then filteredfrom 16. The resulting 'p-phenylphenoxydihydronoras a viscous paleyellow oil which rapidly crystallized. On recrystallization fromethanol,.- it

. formed colorless crystalsmelting at 119 C-. The yieldwas 32 parts. r I

Erample 18 I liiicyclopentadiene (52.8 arts) wasadded am ually to astirred solution of 81.8 parts of 2- chloro-fi-phenylphenol, partsofethylene div chloride, and 2 parts of BFa-diethyl ether at 30-35 C. Themixture was stirred for two hours at 30 C., then washed with hot waterand with soda-solution, dried,'and distilled in vacuo. The2-chloro-6-phenylphenoxydihydronordicyclopene tadiene boiled at 215-220?gradually crystallized and, after severalrecryst'allizations,formed'colorless crystals having a melting point of60-6l C. I V

To a stirred solution of lOO parts of ethylene dichloride; '99parts ofcrystalline. tricyclopentadiene, and 94-parts or phenol, there was addedgradually 5 parts of BF'a-diethylethercomplex 7 while the mixture wascooled to 30'35 C. The

' mixture was stirred 'for twenty-foun hours at room temperature-thenwashedrepeatedlywith .40

- phenoxydihydron ortricyclopentadiene over at 200-225 C./3 mm." as apale yellow viscous oil. Upon redistillation, it boiled at 196- mm. in ayield of 65 parts or pure prod-fchlorophenoxydihydronordicyclopentadiene dis- 7 f tilled over-at 195-200 C./2" mm. as a colorless oil."k

Eramiile 1 6 7 a To a stirred solution or 81.8 parts of'2-chloro-S-phe'nylphenol, 2 parts of BFs dlethyl ether, and

. parts of ethylenedichloride, there was grade ually added 52.8 parts ofdicyclopentadiene while the mixture 'was cooled to "3035 C. The mixturewasthen stirred for four hours at 30 C. and

finally washed with hot water and with soda solution'. Theethylenedichloride was then evaporated off in vacuo one. steam bath, and theresidual oil distilled in vacuo The resulting 2-chloro-6-phenylphenoxydihydronordicyclopentadiene distilled at 235 -240C./2 mm. as a'yellow oil in a yield of 51 parts.

erate yields have. been isolated,

hot"water*and finallywith' soda solution. The

ethylene dichloride was-evaporated off and'the residual oil v( parts)distilled in vacuo." The ene to yield the correspondingaryloxydihydronortetraor norpentacyclopentadienes.

In the presence or acid. condensing agents,-- I polycyclopentadienes ofthe formula:

wherein n iszero or a small whole number, such as 1,2, or 3, react withmonohydric phenols to form new aryl ethers of cyclopentadienes. Thereaction involves both an addition reaction and a, rearrangement of theterminal endomethylene cycle of the polycyclopentadiene.

hydroxydihydronorpoly- While the reaction has been shown as occur! ringprimarily with monohydric phenols, it also occurs with polyhydricphenols.

' In the case of some dihydric phenols, definite products in modbut thereaction V C./2 m. m a yield or 51 parts Upon standing in ice-coldethanol, it w distilled Y ,In'the samemanner, phenols can be condensed iwith tetracyclopentadiene or pentacyclopentadiproduct of chlorophenoland dioyclopentadiene,"-

CH CH: l\ CH C ArOH I wherein Ar is an aryl nucleus and n has a valuefrom zero to a small integer. The ethers formed from dioyclopentadienehave the formula I and are characterized by the presence of the arylether group on one terminal cycle and of an oleflnic bond in theopposite terminal cycle of nordicyclopentadienyl nucleus.

Although in the above examples practically pure polycyclopentadieneshave been used, the process shown may also be applied to mixtures ofhydrocarbons which contain or more of the polycyclopentadienes havingtwo double bonds per molecule, such as are obtained in the thermalcracking of petroleum or in the manufacture of -water gas. The reactionof the polycyclopentadienes provides a new means for separating thecomponents of mixtures of unsaturated hydrocarbons and gives new utilityto such products.

I claim:

1. An acid-catalyzed, addition-rearrangement product of an aromaticbenzenoid compound having a phenolic hydroxyl group and a crystallinepolycyclopentadiene having two double bonds and one to fourendomethylene cycles per molecule, said product being adihydronorpolycyclopentadienyl ether of said benzenoid compound.

2. An acid-catalyzed, addition-rearrangement product of a phenol andcrystalline Dolycyclopentadiene having two double bonds and one to fourendomethylene cycles per molecule, said product being a phenyldihydronorpolycyclopentadienyl ether.

3. An acid-catalyzed, addition-rearrangement product of a phenol anddioyclopentadiene, said product being a phenyldihydronordicyclopentadienyl ether.

said product being chlorophenyl dihydronordicyclopentadienyl ether.-

5. An acid-catalyzed, addition-rearrangement product of phenol anddioyclopentadiene, said product being phenyldihydronordicyclopentadienyl ether.

6. An acid-catalyzed, addition-rearrangement product of phenolandtrieyclopentadiene having two double bonds and two endomethylenecycles per molecule, said product being phenyldihydronortricyclopentadienyl ether.

'7. A method of preparing aryloxydihydronorpolycyclopentadienes havingan ether group in an endoethylene cyclopentano group as one terminalcycle and an olefinic linkage in a flve-membered ring as the oppositeterminal cycle of the nor- \polycyclopentadienyl nucleus which comprises4. An acid-catalyzed, addition-rearrangement reacting at 25 to 50 C. inthe presence of an acidic condensing agent -an aromatic benzenoidcompound having a phenolic hydroxyl group and a crystallinepolycyclopentadiene having two double bonds and one to fourendomethylene cycles per molecule.

8; A method of preparing an aryloxydihydronordicyclopentadiene having anether group in an endoethylene cyclopentano group as a terminal cycleand an oleflnic linkage in a fivemembered ring as the oppposite terminalcycle of the nordicyclopentadienyl nucleus which comprises reacting at25 to 50 C. in the presence of an acidic condensing agent an aromaticbenzenoid compound having a phenolic hydroxyl group and a crystallinedioyclopentadiene having two double bonds per molecule.

9. A method of preparing a phenoxydihydronordicyclopentadiene having theformula ArOCmHm, wherein Ar is a phenyl nucleus and C10H13 is adihydronordicyclopentadienyl group, the oxygen atom being attached tothe endoethylene cyclopentano ring thereof, which comprisesreacting inthe presence of an acidic condensing agent at a temperature of 25 to 50C. a monohydric phenol and crystalline dicyclopentadiene.

10. A method of preparing a phenoxydihydronortricyclopentadiene having aphenyl ether group attached to an endoethylene cyclopentano group as oneterminal cycle and having an olefinic linkage in a flve-membered ring asthe opposite terminal cycle of the nortricyclopentadienyl nucleus whichcomprises reacting a monohydric phenol with crystallinetricyclopentadiene in the presence of an acidic condensing agent at atemperature of 25 to 50 C.

. HERMAN A. BRUSON.

